EP0699349A1 - Ionic conducting material having good anticorrosive properties - Google Patents
Ionic conducting material having good anticorrosive propertiesInfo
- Publication number
- EP0699349A1 EP0699349A1 EP95914390A EP95914390A EP0699349A1 EP 0699349 A1 EP0699349 A1 EP 0699349A1 EP 95914390 A EP95914390 A EP 95914390A EP 95914390 A EP95914390 A EP 95914390A EP 0699349 A1 EP0699349 A1 EP 0699349A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
- C01B21/0935—Imidodisulfonic acid; Nitrilotrisulfonic acid; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
- H01G11/20—Reformation or processes for removal of impurities, e.g. scavenging
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to an ionically conductive material, its preparation and its uses.
- Electrochemical energy storage systems for example batteries or supercapacitors, which operate with high elementary voltages require electrolytes which have a wide range of stability.
- electro ⁇ lytes are obtained by dissolving one or more solutes (l / mM *) + X ' ⁇ in a dipolar liquid solvent, a solvating polymer or their mixtures.
- M 1 is a cation of valence m such as a proton, a cation derived from a metal (for example Li, Na, K, Mg, Ca, Cu, Zn, La) or an organic cation such as an ammonium ion , a guanidinium ion, a phosphonium ion or a sulfonium ion.
- a metal for example Li, Na, K, Mg, Ca, Cu, Zn, La
- organic cation such as an ammonium ion , a guanidinium ion, a phosphonium ion or a sulfonium ion.
- the anions containing perfluorosulfonyl groups RFS0 2 -, in particular the perfluorosulfonates RpS0 3 - and the perfluorosulfonylimides (RpS02) 2N ⁇ are stable and have a low toxicity and the use of the corresponding ionic compounds has become widespread, in particular for electrochemical generators comprising negative electrodes constituted by metallic lithium, an alloy of li- thium or a lithium-carbon insertion compound.
- the preparation of these ionic compounds is however very expensive, and very particularly the manufacture of compounds containing at least two perfluorosulfonyl groups. In addition, these compounds have a high molecular mass and the mass fraction for a given molality in a solvent is large.
- JP-A-05 283 086 relates to a battery in which the electrolyte contains a cyclic ether as solvent and a salt comprising at least two RpS ⁇ 2 groups, RF being a fluorine atom or a fluoroalkyl group.
- RF being a fluorine atom or a fluoroalkyl group.
- a 0 salt of the type (CF3S ⁇ 2) 2NLi or (CF3S02) 3CLi gives a higher conductivity compared to a salt CF3S ⁇ 3Li by the fact that the presence of a single electron-withdrawing group on the atom neighboring l atom of lithium in CF3S ⁇ 3Li increases the electronic density on this atom, in this case oxygen, 5 and therefore makes ionization, that is to say lieration of Li, more difficult, while in a compound (CF3S02) 2 N Li or (CF3SO2) 3CLi, the presence of the two electron-withdrawing groups on the neighboring atom of lithium decreases the electron density on this atom and therefore promotes the release of the Li ion.
- ionically conductive materials having excellent conductivity properties and of stability can be obtained from fluorinated ionic compounds which comprise at least one group in which a fluorine atom is directly linked to a heteroatom.
- An ion-conducting material of the present invention comprises at least one ionic compound in solution in an aprotic solvent.
- the ionic compound is chosen from the compounds represented by one of the formulas (l / mM) + [(ZY) 2 N] ", (l / mM) + [(ZY) 3C] -, (1 / mM) + [(ZY) 2 CQ] ⁇ , in which: Y represents SO2 or POZ; Q represents -H, -COZ or Z; each substituent Z independently represents a fluorine atom or a perfluorinated organic group or not which optionally has at least one polymerisable function, at least one of the substituents Z representing a fluorine atom;
- M represents a cation chosen from the proton and the ca ⁇ tions derived from an alkali metal, an alkaline earth metal, a transition metal, zinc, cadmium, mercury, a rare earth; or from diazonium ions, phosphonium ions, sulfonium ions or oxonium ions; or from the organic cations NuR +, in which Nu is chosen from ammonia, alkylamines, pyridines, imidazoles, amidines, guanidines, alkaloids and R represents hydrogen, an alkyl group or a oxaalkyl group preferably having from 1 to 20 carbon atoms, or an aryl group preferably having from 6 to 30 carbon atoms, methyl, ethyl, propyl, lauryl and methoxyethyl groups being very particularly preferred.
- the ionic compound used for the preparation of the ionically conductive material comprises two FSO2- substituents.
- the publications of the prior art suggest that the replacement of a perfluoroalkyl group by a fluorine atom in a salt causes a reduction in the dissociation of said salt, and that in addition, an FS bond was less stable than a CF bond, all other things being identical, the inventors surprisingly found that the ionic compounds used in the ionically conductive materials of the present invention have great chemical stability as well as electrochemistry in aprotic environments, despite the existence of SF bonds. Such compounds consequently exhibit a wide range of stability with respect to oxidation-reduction phenomena.
- the conductivity of these ionic compounds in solution in aprotic solvents or in solvating polymers or in their mixtures is at least comparable, or even higher than that of the ionic compounds conventionally used or those of derivatives of [RFSO2NSO2 F] "•
- the ionic compounds of the invention have a lower molecular mass than that of the corresponding perfluoroalkylated compounds and their preparation is more economical because it starts from industrial products.
- Z can be chosen from C1-C30 alkyl or C1-Cs perhaloalkyl, C6-C12 aryl or perhaloaryl radicals, aryl-alkyl radicals, oxaalkyl, azaalkyl, thiaalkyl radicals and heterocycles. More particularly, when Z is an alkyl radical, an aryl-alkyl radical, or a perhalo-alkyl radical having more than 4 carbon atoms, the ionic compound of the present invention has surfactant properties.
- the ionic compound of the invention has the properties of a liquid crystal.
- the polymerizable function of the substituent Z can be a polymerizable function, for example by the radical route, by the anionic route or by a Vandenberg type reaction.
- the ionic compound of the invention can be incorporated into a network obtained by polycondensation.
- the ionic compound of the invention can be used as a radical initiator.
- the group Z can consist of a polymer chain.
- the ionic compound of the invention can then constitute a polyelectrolyte.
- Group Z can be a hindered phenol or a quinone.
- the compound of the invention then constitutes a free radical trap and exhibits antioxidant properties.
- Z is a chromophore group, for example Rhodamine B
- the ionic compound of the invention is a dye.
- the ionic compound of the invention constitutes a dissociating dipole.
- 5 Z can also comprise a redox couple such as for example a disulfide, a thioamide, a ferrocene, a phenothiazine, a bis (dialkylamino) aryl, a nitroxide, an aromatic imide.
- Z can also be an electronically doped or self-doping conductive polymer.
- Z can also constitute a complexing ligand or a zwitterion.
- Z can also be a hydrolyzable alkoxy ⁇ ilane, an amino acid, an optically or biologically active polypeptide.
- radicals R 1 , R 2 and R 3 which are identical or different, are chosen from polymerizable non-perfluorinated organic radicals; - R F is chosen from perfluoroalkyl radicals and perfluoroaryl radicals.
- the perfluoroalkyl radicals having from 1 to 8 carbon atoms are preferred, and more particularly the perfluoroalkyl radicals having from 1 to 4 carbon atoms.
- the perfluoroaryl radicals having from 6 to 8 carbon atoms are preferred, for example the perfluorophenyl radical.
- the polymerizable non-perfluorinated organic groups R 1 , R 2 and R 3 allow polymerization reactions by radical, anionic, cationic or stereospecific route, or by polycondensation. They can be chosen from those which comprise double bonds, for example double bonds of the vinyl, allyl, vinylbenzyl or acryloyl type. They can also be chosen from those which contain oxirane or oxetane functions. In addition, they can be chosen from those which contain alcohol, thiol, arylamine, isocyanate or trialkoxysilane functions. They can also be chosen from those which include functions allowing electropolymerization.
- An ion-conducting material of the present invention comprises at least one ionic compound as described above and at least one aprotic solvent.
- the solvent can be an aprotic liquid solvent, chosen for example from linear ethers and cyclic ethers, esters, nitriles, nitrates, amides, sulfones, sulfolanes and sulfonamides.
- Particularly preferred solvents are diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, dimethyltetrahydrofuran, methyl or ethyl formate, propylene or ethylene carbonate, butyrolactones, acetonitrile, benzonitrile, nitromethane, nitro- benzene, dimethylformamide, diethylformamide, N-methylpyrrolidone, dimethylsulfone, tetramethylene sulfone and tetraethylsulfonamide.
- the solvent can also be chosen from solvating polymers, crosslinked or not, bearing or not grafted ionic groups.
- a solvating polymer is a polymer which comprises solvating units containing at least one heteroatom chosen from sulfur, oxygen, nitrogen and fluorine.
- solvating polymers mention may be made of polyethers of linear, comb or block structure, whether or not forming a network, based on poly (ethylene oxide), or the copolymers containing the oxide motif d 'ethylene or propylene oxide or allylglycidylether, polyphosphazenes, crosslinked networks based on polyethylene glycol crosslinked by isocyanates or networks obtained by polycondensation and carrying groups which allow the incorporation of crosslinkable groups. Mention may also be made of block copolymers in which certain blocks carry functions which have redox properties. Of course, the above list is not exhaustive, and all polymers with solvating properties can be used.
- An ionically conductive material of the present invention may simultaneously comprise an aprotic liquid solvent chosen from the aprotic liquid solvents mentioned above and a solvating polymer solvent. It can comprise from 2 to 98% of liquid solvent.
- the solvent for an ion-conducting material of the present invention can also be constituted essentially by a non-solvating polar polymer comprising units containing at least one heteroatom chosen from sulfur, oxygen, nitrogen and fluorine, and with an aprotic liquid chosen from the aprotic liquid solvents mentioned above.
- a non-solvating polar polymer mention may be made of a poly (acrylonitrile), a poly (fluorovinylidene) or a poly (N-vinylpyrrolidone).
- the proportion of aprotic liquid in the solvent can vary from 2% (corresponding to a plasticized solvent) to 98% (corresponding to a gelled solvent).
- An ion-conducting material of the present invention may also contain a salt conventionally used in the prior art for the preparation of an ion-conducting material.
- the ionic compound of the invention also plays the role of passivation additive for the cathode collector, for example when the ionically conductive material is used in a rechargeable lithium generator, the cathode of which has an aluminum collector.
- salts which can be used in admixture with an ionic compound according to the invention, very particularly preferred is a salt chosen from perfluoroalkanesulfonates, bis (perfluoroalkylsulfonyl) imides, bis (perfluoroalkylsulfonyl) methanes and tris (perfluoroalkylsulfonyl) methanes.
- an ionically conductive material of the invention can also contain the additives conventionally used in this type of material, and in particular a plasticizer, a filler, other salts, etc.
- An ionic compound (1 / mM) + [FS02NS02Z] - of the present invention in which Z represents a fluorine atom or an RF perfluoroalkyl radical, can be prepared by reacting the corresponding acid [FS02NS02Z] H in a non-reactive aprotic solvent on a salt of the cation M which is chosen so as to form, during the reaction, a volatile or insoluble acid in the reaction medium and the basicity of which is sufficiently weak not to affect the SF bond.
- the reaction can advantageously take place according to the following reaction scheme:
- the aprotic solvent can be chosen from nitrates, nitroalkanes, esters and ethers.
- Acetonitrile is a particularly preferred solvent because of its volatility and stability.
- the salt used to react with the starting acid and capable of releasing a volatile acid can be chosen from fluorides, chlorides, acetates, tri- fluoroacetates. Fluorides, which do not react on the fluorosulfonyl group and which produce the volatile acid HF are particularly preferred.
- the salt used to react with the starting acid and which makes it possible to obtain an insoluble acid can be chosen from the salts of organic diacids or polyacids by choosing a stoichiometry such that the product formed is an acid salt insoluble in aprotic solvents.
- a stoichiometry such that the product formed is an acid salt insoluble in aprotic solvents.
- oxalates, malonates, polyacrylates, crosslinked or non-crosslinked polymethacrylates, polyphosphates and zeolites mention may be made of oxalates, malonates, polyacrylates, crosslinked or non-crosslinked polymethacrylates, polyphosphates and zeolites.
- Each of the compounds (l / mM) + [(ZY) 2N] -, (1 / mM) + [(ZY) 3C] -, (l / mM) + [(ZY) 2CQ] ⁇ (in which Y represents SO2 or POZ; Q represents -H, -COZ or Z, each substituent Z independently representing a fluorine atom or a perfluorinated organic group or not which optionally has at least one polymerizable function, at least one of the substituents Z representing a fluorine atom as defined previously, M being as defined above) can be prepared by an analogous process starting from the acid corresponding to H [(ZY) 2N], H [(ZY) 3C] or H [(ZY) 2CQ].
- the process described above for preparing the ionic com ⁇ posed the present invention is particularly advantageous in * the extent that it allows to obtain the salts of small cations, and in particular lithium salts which have been obtained by the methods of the prior art.
- lithium generator is intended to mean a generator in which the negative electrode contains lithium, the negative electrode possibly being constituted by metallic lithium, a lithium alloy or even a lithium ion that is inserted, for example LiC ⁇ . In the last two cases, the generator is of the rocking chair type, in which each of the electrodes is a lithium insertion compound.
- the material can also be used as an electrolyte in a supercapacitor.
- a supercapacitor is an electrochemical system comprising an electrolyte and electrodes constituted by carbon or by another inert material of high specific surface, or also by a conjugated redox polymer of the polyacetylene, polyaniline or polythiophene type.
- a material of the invention can also be used for the p or n doping of an electronically conductive polymer.
- a poly (3-phenylthiophene) filr is electrochemically doped in a solution of one of the ionic cores (l / mM) + [(ZY) 2N] ** , (l / mM) + [(ZY) 3C] -, (1 / nM) * [(ZY) 2CQ - (in which Y represents SO2 or POZ; Q represents -H, -COZ or Z, each substituent Z representing independently a fluorine atom or a perfluorinated or non-fluorinated organic group which optionally has at least one polymerizable function, at least one of the substituents Z representing a fluorine atom as defined above, M being as defined above) in a liquid solvent and in a solvating polymer.
- the polymer thus doped can be used as an electrode material in a supercapacitor as mentioned above.
- An ion-conducting material of the invention can also be used in an electrochromic system.
- An ionic compound of the invention can also be used as a constituent of electrolytes melted at low temperature, and in particular of electrolytes which comprise a polymer allowing them to be given plastic or elastomeric properties.
- the ionic compounds of the invention in which the cation is a quaternary imidazolium are particularly suitable for this application.
- the solution was concentrated using a rotary evaporator and the salt was obtained in anhydrous form by treatment under primary vacuum.
- LiFSI Bis (fluorosulfonyl) lithium imide
- the LiFSI salt obtained in Example 1 was dissolved in a polyether and the electrolyte thus obtained was subjected to di- for measures.
- the polyether used is an ethylene oxide copolymer containing approximately 80% of ethylene oxide units. Such a copolymer is described for example in EP-A-0 013 199 or in US-A-4 578 326.
- FIG. 1 represents the DSC curves, noted a), b) and c), obtained respectively after exposure to 90 ° C, 140 ° C and 160 ° C.
- the temperature T expressed in ° C is plotted on the abscissa; the thermal flux FT, expressed in arbitrary units, is plotted on the ordinate.
- LiFSI salt was dissolved in the propylene carbonate used as aprotic solvent in most generators with liquid electrolyte as well as as an additive in certain polymer electrolytes in order to increase the ionic conductivity thereof.
- the conductivity values determined, and especially the conductivity / molecular weight ratio of the LiFSI salt of the invention compare advantageously with those of the LiTFSI salt of the prior art, and a fortiori, with those of the lithium triflate reputed to be less conductive LiTFSI.
- Each of the cells consists of a lithium anode having a thickness of 30 microns, a polymer electrolyte having a thickness of 30 microns and a composite cathode comprising approximately 40% of vanadium oxide, approximately 10% of acetylene black and about 50% of an ethylene oxide copolymer, the proportions being expressed by volume.
- the cathode which has a capacity close to 5-6 C / cm2, is coated on a thin nickel collector.
- the pile has an active surface of 3.89 cm2. It was assembled by hot pressing at 80 ° C.
- the electrolyte contains the LiFSI salt, the average concentration of LiFSI salt in the battery corresponding to an O / Li ratio of 54/1.
- the salt of the electrolyte in cell No. 3 is LiFSI with an O / Li ratio of 30/1.
- FIG. 4 represents the curves of cycling of batteries No. 1 and No. 2.
- the cycling curve gives the percentage of use (% U) of the cathode (on the assumption of 1 Li atom per vanadium atom) as a function of the number of cycles N.
- the cycling curve of the battery N ° l (curve a in FIG. 4) is quite comparable to that of cell No. 2 (curve b, FIG. 4) after 30 complete charge / discharge cycles, and the slow decay slope of l
- the use is substantially the same in both cases, except for the precision of the experimental measurements.
- the initial rate of use of the cathode slightly higher in the case of curve B), results from a higher salt concentration.
- Battery No. 3 gives substantially the same results over 50 cycles, but has a utilization rate identical to that of curve b) obtained by battery No. 2 containing LiTFSI at the same concentration.
- the initial impedance and the impedance after battery cycling remain low and less than 15 ⁇ after cycling.
- EXAMPLE 5 A rechargeable lithium battery was produced, in which the electrolyte contains a second salt (LiTFSI) in addition to a salt (LiFSI) of the invention.
- the battery is of the type:
- the cycling performance of this cell was compared with that of an analog cell containing only LiTFSI.
- FIG. 5 represents the curves of the cycling of the two stacks.
- the cycling curve gives the percentage of use (% U) of the cathode (on the assumption of 1 Li per V) as a function of the number of cycles N.
- the curve b) relates to the cell containing the mixture of salts and curve a) relates to the battery containing only LiTFSI. After nearly 300 deep discharge cycles at 60 ° C., the percentage of use of the cathode is more stable and above all 1 • impedance after cycling remains below 90 ⁇ for the cell according to the invention containing the mixture of salts, while the impedance of the battery containing only LiTFSI is greater than 300 ⁇ .
- LiFSI in principle less stable than LiTFSI
- electrolyte containing LiTFSI facilitates the formation on the aluminum collector, of a fluorinated passivation film which does not interfere with the conductivity.
- the film formed seems very thin, of the order of a few tens or a few hundred nanometers, because observation with a scanning microscope (SEM) of the aluminum surface after cycling and washing does not show significant surface attack aluminum, despite the difference observed between the impedance values for the two batteries compared.
- SEM scanning microscope
- a primary lithium cell operating at room temperature was produced, in which the electrolyte contains the salt (LiFSI) of the invention, a polymer solvent similar to that of the preceding examples, but plasticized by addition of propylene carbonate (PC ).
- the salt (LiFSI) of the invention a polymer solvent similar to that of the preceding examples, but plasticized by addition of propylene carbonate (PC ).
- the battery is of the type: Li °
- the battery has a very stable open circuit voltage (OCV) as a function of time over more than two weeks, which confirms the absence of self-discharge or side reactions.
- the discharge curve presents a regular plateau typical of a cathode of the Mn ⁇ 2 type whose voltage average is 2.8 volts.
- the percentage of use (on the assumption of 1 Li per Mn) of the cathode of this cell which has a capacity of 5.69 C / cm2 and an area of 3.86 cm2 represents 75% of the active material .
- the result confirms the electrochemical compatibility of the salts of the invention in the presence of a liquid electrolyte, used in the present case in the form of a plasticizer for a polymer electrolyte.
- the cost, electrical conductivity and molar mass factors associated with the salts of the present invention therefore present significant advantages over the salts known and used in the prior art in lithium or sodium generators. These advantages are valid both for liquid electrolytes and for plasticized or unplasticized polymer electrolytes, as well as for generators using metallic or alloyed anodes, or generators of the rocking chair type, in particular generators of the lithium type. ion, such as those using LiCô-
Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9403277A FR2717612B1 (en) | 1994-03-21 | 1994-03-21 | Ionic compound carrying a fluorosulfonyl substituent, its use for the preparation of an ionically conductive material. |
FR9403276 | 1994-03-21 | ||
FR9403277 | 1994-03-21 | ||
FR9403276A FR2717620A1 (en) | 1994-03-21 | 1994-03-21 | Additive limiting the corrosion of the collector in an electrochemical cell. |
PCT/FR1995/000343 WO1995026056A1 (en) | 1994-03-21 | 1995-03-21 | Ionic conducting material having good anticorrosive properties |
Publications (2)
Publication Number | Publication Date |
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EP0699349A1 true EP0699349A1 (en) | 1996-03-06 |
EP0699349B1 EP0699349B1 (en) | 2007-10-10 |
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Application Number | Title | Priority Date | Filing Date |
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EP95914390A Expired - Lifetime EP0699349B1 (en) | 1994-03-21 | 1995-03-21 | Ionic conducting material having good anticorrosive properties |
Country Status (6)
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US (3) | US5916475A (en) |
EP (1) | EP0699349B1 (en) |
JP (2) | JP3878206B2 (en) |
CA (1) | CA2163336C (en) |
DE (1) | DE69535612T2 (en) |
WO (1) | WO1995026056A1 (en) |
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WO1995026056A1 (en) | 1995-09-28 |
US20010025943A1 (en) | 2001-10-04 |
DE69535612T2 (en) | 2008-07-24 |
JP2006210331A (en) | 2006-08-10 |
JPH08511274A (en) | 1996-11-26 |
CA2163336A1 (en) | 1995-09-28 |
JP3878206B2 (en) | 2007-02-07 |
DE69535612D1 (en) | 2007-11-22 |
EP0699349B1 (en) | 2007-10-10 |
CA2163336C (en) | 2006-05-09 |
US6682855B2 (en) | 2004-01-27 |
US6254797B1 (en) | 2001-07-03 |
US5916475A (en) | 1999-06-29 |
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